Preparation of halogenated ketones



Patented Sept. 12, 1967 This invention relates to a process for the preparation of perhalogenated cyclohexanones and perhalogenated cyclopentanones.

The preparation of a novel pounds having the formula:

class of chemical com- Wherein X may be F or Cl and It may be 0 or 1, is disclosed in co-pending, commonly assigned application of Louis G. Anello and Richard F. Sweeney, Serial No. 420,154, filed December 21, 1964, which application is in turn a continuation-in-part of co-pending, commonly assigned application of Louis G. Anello and Richard F. Sweeney, Serial No. 381,229, filed July 8, 1964, now abandoned.

Compounds embraced by Formula I are characterized by being perhalogenated cyclohexanones and cyclopentanones, the halogen atoms being fluorine or chlorine, there being present a minimum of two of each, ring-substituted in the molecule. These compounds are useful as sealing adjuvants for films of polytrifiuorochloroethylene.

The process disclosed in the above mentioned applications for the preparation of the ketone compositions of Formula I involves the photochlorination of the corresponding 1-ch-loro-2-alkoxy-perhalogenated cycloal-kenes at temperatures in the range of about 25 C.-l50 C.

It is an object of this invention to provide an alternate route to perhalogenated cyclohexanones and cyclopentanones of the type indicated by Formula I.

Other objects and advantages of the invention will become apparent from the following description.

It has been found that the compounds of Formula I may be prepared by reacting ethers of the formula:

II CF; 01

OX2 wherein X and n are as defined in Formula I and m may be 1 or 2, with cone. H 80 The reaction proceeds smoothly and the perhalogenated ketone products are obtained from the corresponding ether starting materials in conversions of about 7090% and higher.

Ethers of the formula:

III

X211 $11 XgC the replacement of one or two hydrogen atoms with chlorine atoms in compounds of the type indicated by Formula III, will result in intermediate ether products which can be cleaved to the corresponding perhalogenated cyclic ketone products, with cone. H 30 in high conversions. (The intermediate ether products are represented by Formula H.)

The discovery that chlorine substitution in the methyl group, of such ethers as defined by Formula IH, greatly increases the ease and percent of conversion of such materials to the corresponding perhalogenated ketones, by treatment with cone. H is highly unexpected in view of the known state of the art, which indicates that as a general rule, H 80 is not effective in the cleavage of ethers, and particularly in view of the teachings in the art that cleavage of ethers takes place with more difliculty and less efficiency, if at all, as a given ether molecule becomes more highly chlorinated.

For example, it is reported by Robert L. Burwell, Jr., Chem. Rev., vol. 54, p. 662 (1954), that sulfuric acid is not of much use in the cleavage of ethers This is accounted to what the author refers to as the relatively slight nucleo-philic displacing tendency of the bisulfate ion. Strong H 80 he reports, is not effective because conjunct polymerization results. A number of other workers have reported that a variety of ethers are chemically and thermally stable and resist attack by H 80 R. A. Shepard et al., J. Org. Chem., vol. 23, p. 2011 (December 1958), report that materials such as trichloromethyl ether and l-chloro-2-ethoxyhexafluorocyclopentene are very stable materials and resist attack by H 50 J. D. Park et al., J. Org. Chem, vol. 23, p. 1474 (1958) report that chlorinated ethers of the type are stable compounds resistant to hydrolysis in the presence of H 80 As suggested by some of the above noted authors and from a study of their findings, it can be concluded that, as a general rule, the more highly chlorinated a given ether, the more resistant it is to cleavage and that this is particularly true when it is attempted to use H 804 as the cleaving agent. For example, R. A. Shepard et al., supra, report that a non-chlorinated ether, such as ethyl ether, is attacked by H 80 whereas trichloromethyl ether is extremely stable and resists attack by this acid. K. E. Rapp et al., J. Amer. Chem. Soc., vol. 74, p. 749 (February 5, 1952), report that the cleavage of chlorinated polyfluoroalkyl ethers takes place with aluminum chloride (a much more effective cleaving agent than sulfuric acid); but also report that cleavage of these materials takes place at a much slower rate than the rate at which the corresponding unchlorinated parent ethers are cleaved with the same reagent. Conc. H 80 had no hydrolyzing effects on the chlorinated polyfluoroalkyl ether compositions. J. D. Park, in a publication in conjunction with other workers, J. Amer. Chem. Soc., vol. 76, p. 1387 (1954), reports that chlorinated ethers of the type CCl CCl -O-CF CFCl are very stable compounds which undergo none of the reactions to which (nonchlorinated) alkyl and (lesser chlorinated) chloroalkyl ethers are usually susceptible, such as hydrolysis in the presence of H 80 In view of the above-described state of the art, it was entirely unexpected to find that chlorine substitution in the ethers of Formula III, of the order indicated hereinbefore, would result in intermediates which will readily cleave with H 80, to the corresponding perhalogenated cyclic ketones, with high conversions and more surprising, with higher conversions than those obtained when the corresponding unsubstituted ethers of Formula II are employed.

It has been found that a broader range of perhalogenated cyclic ketones'than those embraced by Formula I and disclosed in the above-noted co-pending applications, may be prepared according to the invention process.

The broader range of compounds may be represented by the following formula:

wherein X may be F or Cl and it may be or 1, there being at least one fluorine atom present in the molecule.-

The starting materials employed to produce the compounds of Formula IV may be represented by the following formula:

wherein X and n are as defined in Formula II. The methoxyperhalogenated cycloalkene starting materials are normally liquids at room pared ,by reacting the corresponding dichloro-perhalogenated cycloalkene, wherein two chlorine atoms are temperature and may be previcinally attached to the unsaturated carbon atoms, with an alkali metal alkoxide. The type reaction is more fully described in co-pending, Richard F. Sweeney, Ser. 348,277, filed Feb. 28, 1964 andiscarried out in a reaction'medium comprising a polar solvent, preferably in alkanol corresponding to the alkali metal alkoxide starting material employed, at temperatures from about 0 to about 90 C.

The starting materials of Formula V may be prepared by photochlorinating, at low temperatures, methoxyperr halogenated cycloalkenes having the formula:

VII OX2 wherein X and n correspond to the values and meanings of the compounds of Formula V. The methoxyperhalogenated cycloalkene starting materials of Formula VII may be prepared by an analogous procedure to that described for the preparation of the methoxyperhalogenated cycloalkene. starting materials of Formula VI. Compounds embraced by Formula VII in which the single X atom is F may be prepared by reacting the appropriate perchlorofluorocycloalkene, in which one chlorine atom and one fluorine atom are vicinally attached to the unsaturated carbon atoms, with'an alkali metal alkoxide, as described above. Such perchlorofluorocycloalkenes may be prepared by reacting the corresponding dichloro-perhalogenated commonly assigned application of cycloalkene, wherein two chlorine atoms are vicinally attached to the unsaturated carbon atoms, with HF at temperatures in the range of about 40.0550 C., in the presence of a chromic oxide (Cr O catalyst. The process is illustrated and is more fully described in co-pending,

4 commonly assigned application of Louis GpAnello and Richard F. Sweeney, Ser. No.431,72l, filed Feb. 10, 1965.

Operating temperatures for the photochlorination reaction should be maintained below about 25 C. Some yields of products within the scope of Formulae II and V will be formed at temperatures above about 25 (3., although in progressively decreasing yields as the reaction temperatures increase. At temperatures substantially below about 0 C., the starting materials of Formulae VI and VII, having increased viscosity, will consume chlorine at a muchreduced rate. For optimum results, operating temperatures for the photochlorination reaction should be maintained between about-0 and 10 C.

The photochlorination reaction'can be carried out in an ordinary Pyrex vessel, although a higher photon efliciency can be obtained if a vessel made of quartz or Vycor glass is used. The reaction vessel can be optionally equipped with a gas inlet dip tube, a condenser, a stirrer, a thermometer and heating or cooling means.

The specific light source used in the photochlorination reaction is not critical. The reaction will take place when chlorine gas is passed through the ether starting materials of Formulae VI and-VII, while the reaction mixture is exposed to any source of actinic radiation. Actinic radiation may be definedas the action of any light which eifects chemical change. Thus, any form; of light which etlects chemical reaction may be employed, such as ordinary sunlight, ultraviolet light, commercial incandescent light and fluorescent light. The preferred form of light is ultraviolet which can conveniently be provided by any commercial mercury arc lamp or sun lamp. It has been found that a commercial high pressure mercury arc lamp enclosed in a Vycor Water jacket, which lamp is maintained at a distance of 1 to 3 inches from the reaction vessel, affords a particularly good temperature control although the intensity of the light used is not critical. As a general rule, the speed of the reaction-Will be directly proportional to the intensity of light employed.

Due ,to the relatively low temperatures at which the photochlorination reaction mustbe run, it is important that means be providedior removing the heat generated by the light producing lamps. This can be done by any suitable means and is conveniently accomplished by placing the lamp in a Water cooled Vycor or quartz immersion well, which is set. directly into the reaction vessel. The reaction vessel, in turn, is placed into an ice water cooling bath. Such means also assist in removing reaction exotherm which tends to bring up the temperature in the reactor.

The rate of chlorine addition to the starting materials is determined in part by the efliciency with which the exothermic heat of reaction is dissipated by the cooling means. Higher rates of chlorine consumption require, as will be understood, higher rates of heat removalv from the reaction mixture to maintain reaction temperatures below thedesired 25 C. limit. Thus, the upper limitation on cholorine addition rate is theheat removal the heat exchange equipment used within thereactor volume and the lower limitation on chlorine addition rate is governed by the commensurately longer time which would'be required to complete the reaction at the lower thoxy-compounds (wherein m is 2) and the dichloromethoxycompounds (wherein m is 1), and not the methoxy compounds (wherein m is 3) of Formulae II and V', which are useful according. to the invention process.-.

Depending upon the ratio of chlorine to starting ether employed, the reaction can be controlled selectively to yield products in which the methoxy group is prem-onochlorinated, dichloca acity of Formulae II and V, wherein m is 3. As explained heretofore, it is only the mon-ochlorome.,

rinated, or a mixture of predominantly monochlorinated and dichlorinated products. All that is required to obtain the monochlorinated or dichlorinated products is use of the stoichiometric quantity of chlorine required for monoor dichloro substitution, or a slight excess thereover.

In practice, when a more or less consistent chlorine flow rate is employed, the distribution of the products will depend upon the length of time the chlorination reaction is allowed to proceed. The extent of chlorination in the product can be determined by examining the ratio of the moles of HCl evolved during the photochlorination reaction, to the total moles of starting ether charged. This can be accomplished by weighing the water scrubber or by measuring the amount of HCl absorbed in the water scrubber, such as by the Volhard chloride determination. Generally, it has been found in the case of both the cyclopentyl and cyclohexyl ether starting materials, that when chlorination is effected until about 0.3 moles of HCl per mole of starting ether have evolved, the product mixture consists essentially of the (non-chlorinated) methoxy derivative (i.e. those compounds described by Formulae II and V wherein m i 3). For reasons made apparent by previous discussion, in the H 80 cleavage reaction, it is desirable to employ ether starting materials of the type indicated by Formula III in which at least one chlorine atom is substituted for one of the hydrogen atoms in the methoxy group. It is accordingly desirable to continue the photochlorination reaction until at least approximately 0.7 moles of HCl per mole of starting material are evolved, in which case the product mixture consists of substantial amounts of at least the corresponding monochloromethoxy ether. If the photochlorination reaction is continued until at least 1.3 moles of HCl per mole of starting material are evolved, the product mixture consists of approximately equal proportions of the Corresponding monochloroand dichloromethoxy ethers. It the photochlorination reaction is further continued until about 2.0 moles of HCl per mole of starting material are evolved, the product consists essentially of the corresponding dichloromethoxy ether.

The above described photochlorination process is more fully described in co-pending, commonly assigned application of Richard F. Sweeney, Serial No. 408,391, filed November 2, 1964.

In the event that the various (non-chlorinated) methoxy ether products are recovered in the above described photochlorination reaction to any large extent, or are otherwise available; these materials can be converted to the corresponding monochloromethoxy and dichloromethoxy ether products and mixtures thereof, by the photochlorination procedure described above, which chlorinated ether products are then available for the H 50 cleavage step. The chlorinated ether products, present as monochlorornethoxy ethers, dichloromethoxy ethers, or mixtures thereof, whether obtained directly from the photochlorination of the corresponding unsaturated ethers described by Formulae VI and VII, or whether produced by the photochlorination of the corresponding saturated (non-chlorinated) methoxy ethers described by Formulae II and V, may be used in the H 80 cleavage step without distillation or separation into their individual components.

The cleavage reaction may be carried out with conc. H 50 oleum, S0 or mixtures thereof. There is no critical minimum concentration required for H 80 when used; however, generally, the more dilute the H 80 employed, the larger will be the proportion of ketone product which will be lost due to the reaction of the latter with water present in the reaction mixture. Accordingly, the higher the concentration of H 80 employed, the better will be the results.

Although the term concentrated is a relative one, for the purposes of this paper, it will be considered as referring to at least 60% H 50 It is preferred to use H 50 having a concentration of at least about 95% and best results are obtained when 100% H is employed. Due to the excellent dehydrating properties of 100% H 50 and to the fact that such a reagent contributes little or no water to the reaction mixture; when 100% H 50 is employed, the ketone products are obtained to the virtual exclusion of the ketone hydrates. If less concentrated solutions of H 50 are employed, it is advantageous to add a powerful dehydrating agent, such as phosphorous pentoxide or sulfur trioxide, to the reaction mixture in order to take up any water that may be present.

Oleum consists of H 50 and S0 e.g. so-called 20% oleum consisting by weight of 80% H 80 and 20% free S0 The H 50 component of the oleum will be understood as referring to 100% H 80 concentration. The term oleum as used herein is intended to refer to any mixture of S0 and 100% H 80 Use of oleum containing an S0 strength of about 215% may be used to advantage. There is no upper limit on the S0 strength of oleum which may be employed according to the invention process, since pure S0 may be used. A practical upper limit for S0 strength, when oleum is employed, is about 60%.

In carrying out the cleavage reaction, the cleaving agent is normally added to the ether starting material in an amount at least equal to the stoichiometric. Reaction will take place with less than stoichiometric amounts of cleaving agent, although with diminished conversions. It is desirable to employ an excess of cleaving agent in order to insure completion of the reaction. Very large excesses of cleaving agent will not adversely affect the reaction. When 100% H 80 is employed, for example, molar ratios of H 80 to starting ether in the order of l:l20:1 may be used with expediency. The preferred molar ratio of H 80 to starting ether is in the range of about 1.5:1-521.

The reaction between the cleaving agent and the starting ether must be initiated by the application of heat. At between about 120150 C. reaction takes place as evidenced by the evolution of HCl and care must be taken to control a vigorous exotherm. The reaction should be continued by heating slowly to about l-200 C. at which time the reaction should be substantially complete. Progress and completion of the reaction may be checked by measuring the amount of HCl evolved, such as by the Volhard chloride determination.

The ketone product distills out of the reaction mixture and may be used as is, or be further purified by redistillation from conc. H 80 or without conc. H SO When oleum, and particularly pure S0 is used as the cleaving agent, it is particularly desirable to redistill the ketone product from conc. H 30 to remove S0 which distills over with the ketone.

The following examples illustrate practice of the invention. Parts and percentages are by weight unless otherwise indicated. Percent conversions were computed by dividing the moles of desired ketone product formed by the moles of the ether reactant charged and multiplying by 100.

EXAMPLE 1 The apparatus consisted of a 3%" ID. by 10" round bottom tubular Pyrex reactor, Which was fitted with a Vycor water-cooled immersion well containing a commercial mercury arc light. The reactor is further equipped with an inlet tube at the bottom for chlorine gas and an outlet at the top of the reactor for exit gas. The apparatus was constructed and arranged so that gases exiting from the outlet were passed first through a water cooled condenser and then through a water scrubber and caustic scrubber. The caustic scrubber contained a 10% solution of aqueous sodium hydroxide. The tubular reactor, which was maintained in an ice-water bath so as to control temperatures therein to between about 0 and 5 C., was charged with g. (0.415 mole) of l-chloro-Z-methoxyhexafluorocyclopentane andv hexafluorocyclopentene. 29.8 g. (0.420 mole) of chlorine was passed into the reactor via the inlet tube, over a pe riod of about 2% hours, during which ,time the reactor contents were irradiated with the mercury are light. The are light was positioned about 1" from thereactor. At the end of the reaction period, neither HCl nor unreacted chlorine were detected in vapor exiting from the reactor. The product mixture weighed 120 g. A small sample of the product mixture was chromatographed on a column made up-of Silicone ,(Fluoro) oil, FS,1265 (QF-l), on fire brick at 140 C. The chromatographic analysis showed that the product mixture'was composed of 21 volume percent 1-chloro-2-methoxyhexafluorocyclopentene, llsvolume percent 1-chloro-2-monochlorornethoxyhexafluorocyclopentene, '61 volume. percent 1,1,2-trichloro-2-methoxy- 7 volume percent 1,1,2-trichloro 2 monochlorornethoxyhexafluorocyclopentane. Upon fractional distillation, 31 g. of essentially pure 1,1,2- trichloro-Z-methoxyhexafluorocyclopentane (B1 173 C.) were-recovered from theproduct mixture.

Analysis: Calculated for C H Cl F O: C, 23.11%; H, 0.96%; F, 36.6%; Cl, 34.19%. Found: C, 23.02%; H, 0.80%;F, 36.3%; C1, 33.85%.

The 31 g. of 1,1,2-trichlro-2-methoxyhexafluorocyclopentane, together with 30 g. of 100% H 50 were charged to a 100 ml. three-necked flask,,equipped with a short distillation column, distillation head, thermometer, Dry Ice trap and water trap. The reactant mixture was heated slowly up to about200 C. and distillate boiling in the range of 80-165? C. was collected. Gas-liquid chromatography of the distillate showed that it consisted of 28 volume percent 2,2-dichlorohexafluorocyclopentanone and,

72 volume percent unreacted 1,1,2-trichloro-2-methoxyhexafluorocyclopentane. Based upon the chromatographic data, the conversion of 1,1,2-trichloro-2-methoxyhexafluorocyclopentane to 2,2-dichlorohexafluorocyclopentanone was 28% EXAMPLE 2 was the same as that described in Example 1, except as hereinafter noted. The round bottom tubular reactor was charged with 100 g. (0.42- mole) of 1-chloro-2-methoxyhexafiuorocyclopentene. 89.9 g.

The apparatus used (1.27 moles) of chlorine were passed into the reactor via the inlet tube, over a period of about 12 hours, during which time the reactor contents, as before, were irradiated with the mercury are light. At the end of the reaction period, a total of 16.5 g. of HCl was scrubbed from the vapor exiting the reactor. The product mixture weighed 142.0 g. A small sample of the product mixture was ana.

lyzed by gas-liquid chromatography. The chromatographic analysis showed that the product contained 68.5 volume percent 1,1,2-trichloro-2-monochloromethoxyhexafluorocyclopentane, 23.7 volume percent 1,1,2-trichloro-2-dichloromethoxyhexafluorocyclopentane and 3.5 volume percent 1,1,2-trichloro-2-rnethoxyhexafluorocyclopentane.

fluorocyclopentanone. The conversion to 2,2-dichlorohexafiuorocyclopentanone was 85%.

EXAMPLE 3 A 50 ml. flask, equipped with a 12 cm. micro distillation column and a distillation head, was charged with a mixture of 4.0 g. (0.01 mole) of 1,1,2-trichloro-2-methoxyoctafluorocyclohexane and 40 g. of 96% H 50 The reactant mixture was heated slowly up to about 200 C.

HCl was evolved and product distilled oif. 4 g. of a distillate were recovered, which distillate was shown by infrared spectrum analysis to consist of a mixture of 1,1,2- trichloro-2-methoxyoctafluorocyclohexane starting material and 2,2-dichlorooctafluorocyclohexanone product. Gas chromatographic analysis confirmed the identification of these materials and also showed that the composition of the product mixture was 20 volume percent 2,2-dichloro octafiuorocyclohexanone and volume percent 1,1,2-trichloro-2-methoxyoctafluorocyclohexane. Conversion to 2,2 dichlorooctafluorocyclohexanone was 20%.

EXAMPLE 4 A 200 ml. flask, equipped with a thermowell and.con-' nected to an 18" vacuum'jacket ed distillation column,

which in turn was fittedwith a water-cooled distillation reached about 200 C., at which time the reaction was considered to be complete. A total of 46g. of distillate was obtained from the distillation column. This material was redistilled to give 38 g. (0.12 mole) of 2,2-dich1orooctafluorocyclohexanone (B.P. 1161l7 C.). Identity of the .product was confirmed by infrared analysis and by the following chemical analysis:

Analysis: Calculated for C 'Cl F O: F, 48.87%; Cl,

22.83%..Found: F, 49.0%; C1, 22.9%

The conversion to 2,2-dichlorooctafluorocyclohexanone was 75% EXAMPLE 5 evolved and a product distilled over. The reaction mixture was slowly heated until after .about3 fi1 hours, temperat-ure of the reaction mixture reached about 200 C. The reaction was considered complete at this pointwA total of 315 g. of distillate was recovered. The 315 g. of distil late were redistilled from 96% H 50 to remove traces of S0 From the redistillation, a total of 282 g.v (0.907. mole) of 2,2-dichlorooctafluorocyclohexanone (B.P. 116 C.) was obtained. Identity of this product wasconfirmed by comparison of boiling point data and infrared spectrums. The conversion to 2,2-dichlorooctafluorocyclohexanone was 92%.

When other ether starting materials, or mixtures thereof, within the scope of Formulae II and V are employed the cleavage reaction with either conc. H 50 oleum, S0 or mixtures of these materials, described and the corresponding ketone products are formed with good conversions.

Since those skilled in the art will readily be able to make modifications and innovations over the embodiments described, it should be understood that the inventionis not to be limited except by the scope ofthe appended claims.

proceeds substantially as.

9 We claim: 1. The process for preparing a ketone of the formula:

X210 n ln XzC CCl H 0 wherein X may be P or Cl and n may be 0 or 1, there being at least one fluorine atom present in the molecule; which comprises reacting, at temperatures of at least about 120 C., a starting ether material of the formula: OX2 /o1 C OCH C13-m CCl CX: X wherein X and n are as defined above and m may be 1 or 2, there being at least one fluorine atom present in the molecule, and a cleaving agent selected from the group consisting of H 50 of at least 60% concentration, oleum, S0 and mixtures thereof, and recovering the ketone produced in the reaction.

2. The process of claim 1 in which the cleaving agent is employed in an amount at least equal to the stoichiometric based on the starting ether material.

3. The process for preparing a ketone of the XzC CnXau 0 H 0 wherein X may be P or Cl and 12 may be 0 or 1, which comprises reacting, at temperatures of at least formula:

about 120 C., a starting ether material of the formula:

X21101] o- 0 oHm Ol X 0 Con OX2 wherein X and n are as defined above and m may be and a cleaving agent selected from the group consisting of H 80 of at least 60% concentration, oleum, S0 and mixtures thereof, and recovering the ketone produced in the reaction.

4. The process of claim 3 in which the cleaving agent is employed in an amount at least equal to the stoichiometric based on the starting ether material.

5. The process for preparing a ketone of the formula:

wherein X may be P or Cl and n may be 0 or 1, there being at least one fluorine atom present in the molecule, which comprises:

(a) chlorinating, at temperatures below about 25 C., a

starting ether material selected from the group consisting of 0X, 0X: 01 XhCn COCH3 XnOn OOCH X10 o-X X (3-01 ox, CX:

and mixtures thereof,

10 wherein X and n are as defined above, in the presence of actinic radiation for a period of time sufficient to substantially convert the starting ether material to a reaction product containing an intermediate ether material of the formula:

OX5 C1 C 0 Clinch-us C-- Cl wherein X and n are as defined above and m may be 1 or 2, there being at least one fluorine atom present in the molecule,

(b) reacting, at temperatures of at least about 120 C., the reaction product containing the intermediate ether and a cleaving agent selected from the group consisting of H of at least 60% concentration, oleum, S0 and mixtures thereof, and

(c) recovering the ketone produced in the reaction.

6. The process of claim 5 in which the intermediate ether material is isolated from the reaction product of the chlorination step prior to subsequent reaction with the cleaving agent as described in part (b).

7. The process of claim 6 in which the cleaving agent is employed in an amount at least equal to the stoichiometric based on the intermediate ether material.

8. The process of claim 7 in which the chlorination step of part (a) is carried out until at least about 0.7 moles of HCl per mole of starting ether material is evolved.

9. The process of claim 8 in which the starting ether material of part (a) is a compound of the formula:

Cl and n may be 0 or 1, there fluorine atom present in the Xancn wherein X may be F or being at least one molecule. 10. The process of claim 8 in which the starting ether material of part (a) is a compound of the formula:

Cl and n may be 0 or 1, there fluorine atom present in the wherein X may be F or being at least one wherein X may be F or C1 and 12 may be 0 or 1,

which comprises:

(a) chlorinating, at temperatures below about 25 C., a starting ether material selected from the group consisting of:

C F: C Fa C1 X2 Cu C-OCH3 X1 0 \CZO CH;

X: o o- 01 X; o o 01,

CXa UK:

and mixtures thereof,

wherein X and n are as defined above, in the presence of actinic radiation for a period of time sufiicient to substantially convert the starting ether material to a 1 1 reaction product containing an material of the formula:

or: or

wherein X and n are as defined above and m may be (b) reacting at temperatures of at least about 120 C., the reaction product containing the intermediate ether and'a cleaving agent selectedfromthe group consisting of H 80 of at least 60% concentration, oleum, S and mixtures thereof, and

(c) recovering the ketone produced in the reaction.

12. The process of claim 11 in which the intermediate ether material is isolated from the reaction product of the chlorination step prior to subsequent reaction with the cleaving agent, as. described in'part (b).

13. The process of claim 12 in which the cleaving agent is employed in an amount at least equal to the stoichiornetric based on the intermediate ether material.

14. The process .of claim 13 in' which the chlorination step of part (a) is carried out until at least about 0.7 mole of HCl per mole of starting ether material is evolved.

15. The process of claim 14 in which the starting ether material of part (a) is a compound of the formula:

intermediate ether wherein Xmay beFor Cl and nmay be 0 or 1.

CF: C1

X 0 Cl;

wherein X may be F or Cl and 21 may be 0 or 1.

17. The process for preparing 2,2-dichlorohexafluorocyclopentanone which comprises reacting, at temperatures of at least about 120 C., a starting ether material selected from the group consisting of 1,1,2-trichloro-2-monochloromethoxyhexafluorocyclopentane; 1,l,2-trichloro-2-dichloromethoxyhexafluorocyclopentane and mixtures thereof, and a cleaving agent selected from the group consisting of H 80 of at least-60% concentration, oleum, S0 and mixtures thereof, which cleaving agent is employed in an amount at least equal to the stoichiornetric based on the starting ether material, and recovering the 2,2-dichlorohexafluorocyclopentanone produced in the reaction.

18. The process for preparing 2,2-dichlorooctafluorocyclohexanone which comprises reacting, at temperatures of at least about 120 C., a starting ether material selected frornthe group consisting of 1,l,2-trichlor0-2- monochloromethoxyoctafluorocyclohexane; 1,1,2-trichloro 2-dichloromethoxyoctafiuorocyclohexane, and mixtures thereof, and a cleaving agent selected from the group consisting of H 50 of at least 60% concentration, oleum, S0 and mixtures thereof, which cleaving agent is employed in an amount at least equal to the stoichiornetric based on the starting ether material, and recovering the 2,2-dichlorooctafluorocyclohexanone produced in the reaction.

19. The process for preparing 2,2-dichlorohexafluorocyclopentanone which comprises:

(a) chlorinating a starting ether material selectedfrorn the group consisting of 1-chloro-2-methoxyhexafiuorocyclopentene-l; 1,1,2-trichloro-2-methoxyhexafluorocyclopentane and mixtures thereof, at temperatures below about 25 C., in the presence of actinic radiatiomuntil at leastabout 0.7 mole of HCl per mole of starting ether material is evolved,

(b) reacting, at temperatures of at least about 120 C., thereaction product thus obtained H 50 and having a concentration of at least 60%, which H reactant is used in.an amount at least equal to the stoichiometric based on the reaction product obtained in part (a), and 1 (c) recovering the 2,2-dichlorohexafluorocyclopentanone produced in the reaction.

20.= The process of claim 19 in whichthechlorination step of part (a) isicarried out until at least about 1.3 moles of HCl per mole of starting ether material are evolved.

21. The process cyclohexanone which comprises:

(a) chlorinating a starting ether material selected from thegroup consisting of 1-chloro-2-methoxyoctafluorocyclohexene-l 1,1,2-trichloro-2-methoxyoctafiuorocyclohexane and mixtures thereof, at temperatures below about 25 C., in the presence vof actinic radiation, until at least about 0.7 mole of HCl per mole of starting ether material is evolved,

(b) reacting, at temperatures of at least about 120 C., the reaction product thus obtained and H 80 having a concentration of at least 60%, which H 50 reactant is used in an to the stoichiornetric based on obtained in part (a), and

(c) recovering the 2,2 dichlorooctafluorocyclohexanone produced in the reaction.

22. The process of claim 21 in which the chlorination step of part (a) is carried out until at least about 1.3 moles of HCl per mole of startingv ether material are evolved.

23. The process according to claim 1 in which the H 80, reactant has a concentration of at least 24. The process according to claim 3 in which the H SO reactant has a concentration of at least 95%.

25. The process of clainrS in which the H 80 employed in step (b) has a concentration of at least 95%.

26.. The process of claim 11 in which the H 80 employed in step (b) has a concentration of at least 95%.

27. The process according to claim 17 in which the H 80 reactant has a concentration of at least 95 28. The process of claim 19 in which the H 50 employed in step (b). has a concentration of at least 95 LEON ZITVER, Primary Examiner. M. JACOB, Assistant Examiner.

for preparing 2,2-dichlorooctafiuoro- 1 amount at. least equal the reaction product,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,341,602 September 12, 1967 Louis G. Anello et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 71, for "II" read III column 3, lines 19 to 23, formula V should appear as shown below instead of as in the patent:

same column, lines 30 to 35, formula VI should appear as shown below instead of as in the patent:

line 44, for "Ser. 348,277" read Ser. No. 348,277 same column 3, line 46, for "in" read an column 9, lines 70 to 74, the left-hand formula should appear as shown below instead of as in the patent:

column ll, line 62, for "r0 2-" read ro-Z- column 12, line 15, for "H 50 and" read and H 50 Signed and sealed this 15th day of October 1968.

(SEAL) ATTEST:

EDWARD M .FLETCHER,JR. EDWARD J BRENNER Attesting Officer Commissioner of Patents 

1. THE PROCESS FOR PREPARING A KETONE OF THE FORMULA:
 5. THE PROCESS FOR PREPARING A KETONE OF THE FORMULA: 